TWI609060B - Readily thermally degradable organic resin binder - Google Patents

Description

Immediately thermally decomposable organic resin binder

The present invention relates to an immediate thermally decomposable organic resin binder and to a high concentration inorganic particle dispersion prepared therefrom, which is exemplified by a conductive paste, a metal ink, a ceramic paste. Material, and glass paste.

More particularly, the present invention relates to an immediate thermally decomposable organic resin adhesive which is reduced in the firing step when used as a binder component in a high concentration inorganic particulate dispersion printed or coated on various components. The problem of carbon residue is produced without damaging the printing or coating step. The present invention also relates to a high concentration inorganic fine particle dispersion containing such an immediate thermally decomposable organic resin binder as a binder component.

In the field of electronic components, high-concentration inorganic particle dispersion systems are used as printing inks and coating materials for, for example, circuits, electrodes, photovoltaic panels, microstrip antennas, capacitors, inductors, layered ceramic capacitors, and electricity. In the process of slurry display panels, etc.

When used in the printing or coating step of producing electronic components, the high concentration inorganic particle dispersion enables the manufacture of electronic components to be well and precisely controlled, and thus is used industrially as an enhancement of electronic component characteristics and promotion of electrons. The method of mass production of components.

In a method generally used for producing precisely manufactured components (typically, electronic components), a high-concentration inorganic particulate dispersion system is printed or coated using a printer or a coater, followed by fire baking. For example, the circuit pattern can be formed on the substrate immediately by printing a circuit by screen printing using a conductive paint in which metal particles are dispersed; drying; and then baking. Further, a protective layer or an insulating layer can be formed immediately on a large area by coating with a coater in which metal oxide particles are dispersed by a coater; drying; and then baking.

When a high concentration inorganic fine particle dispersion is used in a printing step or a coating step, the ethyl cellulose resin becomes a commonly used organic resin binder. However, the ethyl cellulose resin has poor thermal decomposability (high thermal decomposition temperature), and as a result, it is easy to leave carbon residue at a low fire baking temperature, which causes a decrease in electrical characteristics of the printed layer or the coating layer.

There is a need to reduce the temperature of the firing step and the time required to shorten the firing step, based on current improvements in production efficiency and energy efficiency. In addition, the lower weight and smaller size brought about by the advancement of production technology are required for the assembly, and the substrate is made thinner and converted into plastic, so that the firing step pursues lower temperature and shorter time. .

These problems have been sought by replacing ethyl cellulose resins as organic resin binders with (meth)acrylic resins, polyepoxyalkylene resins, and the like which have excellent low temperature decomposability. However, the use of this technique can still cause defects during printing, which does not provide a complete answer to these questions.

In the inventions described in Patent Documents 1, 2, and 3 (see below), a (meth)acrylic resin is used as an organic resin binder to reduce the fire-residue residue. However, (meth)acrylic resin binders have strong spinnability or fiberiness, which causes confusion in the final area of printing. Further, the (meth)acrylic resin binder has a lower viscosity than the ethylcellulose resin binder, which causes a problem of a low aspect ratio of the pattern. This aspect ratio represents the height-to-width ratio of the circuit pattern. For example, in the case of photovoltaic cells, the electrodes preferably have a narrower width and a higher height to relax the area where the light is received. This situation is called a high aspect ratio.

Prior technical literature Patent literature

Patent Document 1 JP 2013-235678 A

Patent Document 2 JP 3632868 B

Patent Document 3 JP 4573696 B

SUMMARY OF THE INVENTION An object of the present invention is to provide an immediate thermal decomposable organic resin adhesive which can be fired in comparison with an ethyl cellulose resin which is generally used as an organic resin binder for a high concentration inorganic fine particle dispersion. It is carried out at low temperatures and supports a greater pressing effect on carbon residue while maintaining printing characteristics. It is an additional object of the present invention to provide a high concentration inorganic particle dispersion containing the organic resin binder.

The inventors of the present invention have found that an immediate thermally decomposable organic resin binder capable of achieving the above object is obtained by mixing a (meth)acrylic resin represented by the following general formula (1) with an ethyl group. The cellulose resin is provided in a weight ratio of (meth)acrylic resin to ethylcellulose resin of from 5:95 to 50:50.

The inventors of the present invention made the following inference, and this does not mean that the functional mechanism of the immediately thermally decomposable organic resin binder of the present invention is clear: (meth)acrylic resin and ethylcellulose resin in a high concentration inorganic The fine particle dispersion exhibits a microphase separation state containing inorganic fine particles and the immediately thermally decomposable organic resin binder of the present invention, and optionally contains an organic solvent and an additive. In the firing step, the microphase-separated structure disintegrates when the highly thermally decomposable (meth)acrylic resin begins to decompose, and promotes decomposition of the ethylcellulose resin, and as a result, the thermal decomposability is improved beyond that only by B. Thermal decomposability of an organic resin binder composed of a cellulose resin.

Due to the formation of such a microphase-separated structure, the structural viscosity of the ethyl cellulose resin is suppressed, and the fiber properties of the (meth)acrylic resin are suppressed, and since this is improved, the parallel alignment is improved, and the surface of the screen printing can be improved. Degree and precision.

The high concentration inorganic particle dispersion containing the immediate thermally decomposable organic resin binder of the present invention as a binder component can reduce oil removal during the firing step after the dispersion is printed or coated on any of the various components. The problem caused by insufficient or carbon fragmentation, Such problems are, for example, a decrease in conductivity characteristics or a decrease in component strength. As a secondary effect, by mixing ethyl cellulose resin and (meth)acrylic resin in an appropriate weight ratio, the fiber properties due to the properties of the (meth)acrylic resin can be suppressed and the printing precision can be prevented. Degree is reduced.

The immediate thermal decomposable organic resin binder of the present invention and the high concentration inorganic fine particle dispersion system are described in detail below.

1. Immediately thermally decomposable organic resin

The immediate thermally decomposable organic resin binder of the present invention provides a weight ratio between a (meth)acrylic resin and an ethylcellulose resin by mixing a specified (meth)acrylic resin and an ethylcellulose resin. Obtained for 5:95 to 50:50 and has the ability to reduce the amount of carbon slag produced during the firing step, relative to the amount of carbon residue produced by the ethylcellulose resin binder.

The (meth)acrylic resin used in the present invention is an acrylic polymer having a monomer unit represented by the following general formula (1) [C1]

[In the formula, R ¹ represents hydrogen or methyl, and R ² represents hydrogen or C _1-12 , especially a C _1-4 linear hydrocarbon group, a branched hydrocarbon group, or a hydrocarbon group having a hydroxyl group, or a poly ring-containing ring Polyalkylene oxide-containing group].

The monomer constituting the (meth)acrylic resin may, for example, be (meth)acrylic acid; an alkyl ester of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate Ester, n-amyl (meth)acrylate, isoamyl (meth)acrylate, neopentyl (meth)acrylate, third amyl (meth)acrylate, n-hexyl (meth)acrylate, (methyl) ) isohexyl acrylate, n-octyl (meth)acrylate, third octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; (meth)acrylic acid a hydroxyalkyl ester such as hydroxyethyl (meth) acrylate; a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate (meth)acrylic acid polyalkylene glycol esters such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, etc.; and alkoxy polyalkylene (meth)acrylate Glycol esters, such as (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol and the like. These can be used singly or in combination.

The (meth)acrylic resin has a weight average molecular weight of 1,000 to 250,000 and preferably 2,000 to 200,000. When the weight average molecular weight of the (meth)acrylic resin is less than 1,000, the viscosity suitable for screen printing and the adhesion to the printed substrate cannot be obtained, and the accuracy of the circuit pattern may be lowered. When the weight average molecular weight of the (meth)acrylic resin exceeds 250,000, the compatibility with the ethyl cellulose resin is lowered, and an appropriate degree of thermal decomposition promoting behavior of the object of the present invention cannot be obtained.

This (meth)acrylic resin is preferably obtained by a solution polymerization method. The (meth)acrylic resin obtained by the emulsion polymerization method is not desired because the electrical properties may be destroyed by the alkali metal derived from the emulsifier used, and because the interface may be caused by the interface orientation of the emulsifier component. The adhesion is reduced.

The ethyl cellulose resin used in the present invention is an ethylene derivative of cellulose, and is commercially available in various grades. Examples herein are STD-4, STD-7, STD-10, STD-20, STD-45, and STD-100 from Dow Chemical Company. However, the ethyl cellulose resin used in the present invention is not limited to these product numbers.

Since the object is to promote blending to obtain a high concentration inorganic fine particle dispersion, the immediate thermally decomposable organic resin adhesive of the present invention may optionally contain an organic solvent. The organic solvent to be used may, for example, be an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a ketone, an ester, an alcohol, an ether, a polyglycol, a terpene or the like. It is preferred to select a solvent suitable for the system used.

The organic solvent can be specifically exemplified by methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, ethylene glycol monomethyl Ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 2,2,4-trimethyl-1 , 3-pentanediol monoisobutyrate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, ethylene glycol monomethyl ether acetate Diethylene glycol monomethyl Ethyl ether acetate, triethylene glycol monomethyl ether acetate, ethylene glycol monoisopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, triethylene glycol monoisopropyl Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, Dipropylene glycol monomethyl ether acetate, decane, n-decane, isodecane, n-dodecane, isododecane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, Toluene, xylene, terpineol, dihydroxy terpineol, and dihydroxy terpineol acetate. One of them may be used alone or a combination thereof may be used.

2. High concentration inorganic particle dispersion

The high-concentration inorganic fine particle dispersion of the present invention has inorganic fine particles and an immediate thermally decomposable organic resin binder as essential components, and has an organic solvent and other additives as optional components, and each component is preferably selected specifically for use in combination.

The inorganic fine particles can be exemplified by gold, silver, copper, aluminum, nickel, cobalt, tin, zinc, lead, tungsten, carbon, rare earth metals, alloys of these metals, alumina, cerium oxide, zirconium oxide, cerium oxide, ferrite. Microparticles of body, zinc oxide, titanium oxide, barium titanate, lead zirconate, boron oxide, boron nitride, tantalum nitride, tantalum carbide, tungsten carbide, etc., which are customarily used for conducting pastes, printing Particle size in ink and paint. One of these may be used alone, or a combination thereof may be used, but the inorganic fine particles are selected to be used in combination with the application.

The content of the inorganic fine particles in the high-concentration inorganic fine particle dispersion of the present invention is not particularly limited, but a preferred lower limit is 30% by weight and a preferred upper limit is 95% by weight. When the inorganic particulate content is less than 30% by weight, The resulting dispersion does not have an appropriate viscosity, and printability and coatability may be lowered. When the content of the inorganic fine particles exceeds 95% by weight, the viscosity of the obtained dispersion may be too high, and printability and coatability may be worse.

The content of the immediate thermally decomposable organic resin binder in the high-concentration inorganic fine particle dispersion of the present invention is not particularly limited, but a preferred lower limit is 0.5% by weight, and a preferred upper limit is 30% by weight. When the content of the resin binder is less than 0.5% by weight, the resulting dispersion does not have an appropriate viscosity, and thus storage stability may be worse, and sedimentation of inorganic particles may occur. When the content of the resin binder exceeds 30% by weight, the amount of organic residue produced increases, and electrical characteristics and mechanical properties may be lowered after the fire-bake step.

In addition to the inorganic fine particles and the immediately thermally decomposable organic resin binder, the high concentration dispersion of the present invention may contain an organic solvent to achieve the goal of adjusting the viscosity of the inorganic fine particle dispersion. Such an organic solvent can be exemplified by methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, ethylene glycol. Monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether, diethylene glycol butyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 2,2,4-trimethyl- 1,3-pentanediol monoisobutyrate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, ethylene glycol monomethyl ether acetate Ester, diethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, ethylene glycol monoisopropyl ether acetate, diethyl Glycol monoisopropyl ether acetate, triethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol Alcohol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, decane, n-decane, isodecane, n-dodecane, isododecane, A Cyclohexane, dimethylcyclohexane, ethylcyclohexane, toluene, xylene, terpineol, dihydroxy terpineol, and dihydroxy terpineol acetate. One of these may be used alone or a combination thereof may be used, but the organic solvent and its incorporated content are preferably formulated for use in a combined use.

The content of the organic solvent to be used is not particularly limited, but is preferably in the range of 0 to 70% by weight based on the weight of the high-concentration inorganic fine particle dispersion. When the content of the organic solvent exceeds 70% by weight, a suitable concentration at which a dispersion is produced cannot be obtained, and printability and coatability are thus deteriorated.

The high-concentration inorganic fine particle dispersion of the present invention may contain, in addition to the inorganic fine particles of the essential component and the immediately thermally decomposable organic resin binder, a dispersion to achieve the object of promoting the dispersion of the inorganic fine particles. The dispersion is not particularly limited as long as it has the ability to disperse inorganic fine particles in a medium, and a commercial dispersion such as an amine compound such as octylamine, hexylamine, or oleylamine; a sulfur compound such as dodecyl sulfur can be used. An alcohol; a carboxylic acid compound such as oleic acid; a branched polymeric compound having an ammonium group; a low molecular weight compound or a high molecular weight compound having a dithiocarbamate; a dendrimer or a superbranched polymer; An ammonium-based hyperbranched polymer; a phosphate-type dispersion; or a polyethyleneimine-grafted polymer-type dispersion. Separate dispersions may be used or two or more may be used in combination.

In addition to the inorganic fine particles and the immediately thermally decomposable organic resin binder, the high-concentration inorganic fine particle dispersion of the present invention may further contain a viscosity adjusting agent to achieve the goal of adjusting the rheological properties at the time of printing. The viscosity modifier is not particularly limited, and a commercially available viscosity modifier containing an inorganic compound such as cerium oxide, bentonite, or calcium carbonate, or an organic compound such as hydrogenated castor oil, an amine, or a polyolefin may be used. , polymeric vegetable oils, and surfactants. A separate viscosity modifier may be used or two or more may be used in combination.

It is known that the improvement of the fiberiness causing printing defects can be obtained by judicious use of the above viscosity adjusting agent. It is preferred to use a suitable viscosity modifier to properly achieve the efficacy of the present invention.

The high-concentration inorganic fine particle dispersion of the present invention may contain other substances such as a surfactant, a leveling agent, a flame retardant, a plasticizer, an adhesion promoter, and coloring insofar as the characteristics and objects of the present invention are not impaired. Agents, antistatic agents, antioxidants, light stabilizers, release agents, and coupling agents.

3. Manufacture of high concentration inorganic particle dispersion

The high-concentration inorganic fine particle dispersion of the present invention can be produced by mixing and kneading inorganic fine particles, a resin binder, an organic solvent, a dispersion, a viscosity modifier, and other necessary components. The kneading step can be carried out by a usual method. The kneading device can be exemplified as a Henschel mixer, a belt mixer, a Nauta mixer, a paddle mixer, a high speed flow mixer, a paint shaker, a roll mill, a ball mill. , grinder, sand mixer, and bead mill.

The application of the high-concentration inorganic fine particle dispersion of the present invention is not particularly limited, and it can be advantageously used for printing patterns such as specifying interconnections, electrodes, resistive elements, capacitors, coils, and the like, or applications for coating, To achieve the goal of imparting specific functionality to electronic components in the production of electronic components, such as circuits, electrodes, photovoltaic panels, microstrip antennas, capacitors, inductors, layered ceramic capacitors, and plasma display panels.

[Examples]

The invention will be specifically described below by way of examples. The invention is in no way limited to or by the embodiments. Unless otherwise specified, "%" and "parts" in the examples mean "% by weight" and "parts by weight".

Example 1

100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 95 ° C while being filled with nitrogen; and 100 parts of a mixture of methyl methacrylate (ACRYESTER from Mitsubishi Rayon Co., Ltd.) M) and a polymerization initiator LUPEROX 219 (3,5,5-trimethylhexyl peroxide from ARKEMA Yoshitomi, Ltd.) were dropped from the dropping device at a fixed rate for 75 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, 2,2,4-trimethyl -1,3-pentanediol monoisobutyrate adjusted the solid ratio to 40% to obtain a (meth)acrylic resin [A-1]. The weight average molecular weight of the synthesized acrylic copolymer was 15,000 as measured by gel permeation chromatography using polystyrene.

Example 2

100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with a stirring device, a thermometer, a reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 155 ° C while being filled with nitrogen; and 200 parts of a n-butyl methacrylate mixture (from Mitsubishi Rayon Co., Ltd.) ACRYESTER B) and a polymerization initiator LUPEROX DTA (di-third amyl peroxide from ARKEMA Yoshitomi, Ltd.) were dropped from the dropping device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-2]. . The weight average molecular weight of the synthesized acrylic copolymer was 8,000 as measured by gel permeation chromatography using polystyrene.

Example 3

100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with a stirring device, a thermometer, a reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 155 ° C while being filled with nitrogen; and 200 parts of a mixture of isobutyl methacrylate (from Mitsubishi Rayon Co., Ltd.) ACRYESTER IB) and polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) was dropped from the drip device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-3]. . The weight average molecular weight of the synthesized acrylic copolymer was 7,500 as measured by gel permeation chromatography using polystyrene.

Example 4

100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 155 ° C while filling with nitrogen; and 200 parts of 2-ethylhexyl methacrylate mixture (from Mitsubishi Rayon Co., Ltd.) ACRYESTER EH) and a polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) were dropped from the dropping device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-4]. . The weight average molecular weight of the synthesized acrylic copolymer was 6,000 as measured by gel permeation chromatography using polystyrene.

Example 5

30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, And nitrogen was charged into the crucible; the temperature was raised to 135 ° C while being filled with nitrogen; and 70 parts of a lauryl methacrylate mixture (ACRYESTER L from Mitsubishi Rayon Co., Ltd.) and a polymerization initiator LUPEROX 570 ( The third amyl-3,5,5-trimethylhexane peroxyester from ARKEMA Yoshitomi, Ltd. was dropped from the dropping device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-5]. . The weight average molecular weight of the synthesized acrylic copolymer was 9,500 as measured by gel permeation chromatography on polystyrene.

Example 6

30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 155 ° C while being filled with nitrogen; and 70 parts of isobutyl acrylate mixture (IBA from Mitsubishi Chemical Corporation) and polymerization initiator were added. LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was dropped from the drip device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-6]. . The weight average molecular weight of the synthesized acrylic copolymer was 14,000 as measured by gel permeation chromatography using polystyrene.

Example 7

30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 155 ° C while being filled with nitrogen; and 70 parts of 2-ethylhexyl acrylate mixture (HA from Mitsubishi Chemical Corporation) and polymerization were carried out. The starter LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was dropped from the drip device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-7]. . The weight average molecular weight of the synthesized acrylic copolymer was 10,000 as measured by gel permeation chromatography using polystyrene.

Example 8

100 parts of butyl carbitol (BDG from Nippon Nyukazai Co., Ltd.) was charged into a 1 liter reaction vessel equipped with a stirring device, a thermometer, a reflux condenser, and a nitrogen gas filled enthalpy; Raised to 155 ° C while being filled with nitrogen; and 200 parts of a mixture of hydroxyethyl methacrylate (ACRYESTER HO from Mitsubishi Rayon Co., Ltd.) and a polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) The drip device was instilled at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. The (meth)acrylic resin [A-8] was obtained. The weight average molecular weight of the synthesized acrylic copolymer was 2,000 as measured by gel permeation chromatography using polystyrene.

Example 9

30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 155 ° C while being filled with nitrogen; and 70 parts of isobutyl methacrylate mixture (ACRYESTER from Mitsubishi Rayon Co., Ltd.) IB) which is a methoxypolyethylene glycol acrylate having a polyethylene glycol segment molecular weight of 400 (AM-90G from Shin-Nakamura Chemical Co., Ltd.) and a polymerization initiator LUPEROX 570 (ARKEMA) Yoshitomi, Ltd.) was dropped from the drip device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-9]. . The weight average molecular weight of the synthesized acrylic copolymer was 20,000 as measured by gel permeation chromatography using polystyrene.

Example 10

30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged to the crucible; the temperature was raised to 155 ° C while filling with nitrogen; and 70 parts of isobutyl methacrylate mixture (from Mitsubishi) ACRYESTER IB) of Rayon Co., Ltd. and a polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) were dropped from the dropping device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-10]. . The weight average molecular weight of the synthesized acrylic copolymer was 2,000 as measured by gel permeation chromatography using polystyrene.

Example 11

100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was charged into a 1 liter reaction vessel equipped with Stirring device, thermometer, reflux condenser, and nitrogen were charged into the crucible; the temperature was raised to 135 ° C while filling with nitrogen; and 200 parts of isobutyl methacrylate mixture (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) And a polymerization initiator LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was dropped from the dropping device at a fixed rate for 90 minutes. After heating and stirring for an additional 4 hours, cooling was allowed to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-11]. . The weight average molecular weight of the synthesized acrylic copolymer was 21,000 as measured by gel permeation chromatography using polystyrene.

Example 12

150 parts of a mixture of isobutyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and a polymerization initiator V59 (2,2-azobis(2-methylbutyronitrile) to Wako Pure Chemical Industries, Ltd.) was charged into a 1 liter reaction vessel equipped with a stirring device, a thermometer, a reflux condenser, and a nitrogen gas charge.埠; the temperature was raised to 80 ° C while being filled with nitrogen; heating and stirring for an additional 4 hours, and cooling to room temperature, and the polymerization was terminated. After the termination of the polymerization, the solid ratio was adjusted to 40% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.). The (meth)acrylic resin [A-12] was obtained. The weight average molecular weight of the synthesized acrylic copolymer was 50,000 as measured by gel permeation chromatography using polystyrene.

Example 13

The 150 parts of isobutyl methacrylate (. From Mitsubishi Rayon Co., Ltd of ACRYESTER IB) and a polymerization initiator V65 (Chemical Industries from Wako Pure, Ltd of 2,2 '- azobis (2, 4-dimethylvaleronitrile)) charged into a 1 liter reaction vessel equipped with a stirring device, a thermometer, a reflux condenser, and nitrogen gas filled with hydrazine; the temperature was raised to 70 ° C while being filled with nitrogen; heating and The mixture was stirred for an additional 4 hours and cooled to room temperature to terminate the polymerization. After the termination of the polymerization, the solid ratio was adjusted to 40% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.). The (meth)acrylic resin [A-13] was obtained. The weight average molecular weight of the synthesized acrylic copolymer was 170,000 as measured by gel permeation chromatography on polystyrene.

Example 14

150 parts of a mixture of isobutyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and a polymerization initiator V65 (Wako Pure Chemical Industries, Ltd.) were placed in a 1 liter reaction vessel equipped with agitation. The apparatus, the thermometer, the reflux condenser, and the nitrogen gas were charged into the crucible; the temperature was raised to 70 ° C while being filled with nitrogen; the mixture was heated and stirred for an additional 4 hours, and cooled to room temperature to terminate the polymerization. After the termination of the polymerization, the solid ratio was adjusted to 30% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.). The (meth)acrylic resin [A-14] was obtained. The weight average molecular weight of the synthesized acrylic copolymer was 240,000 as measured by gel permeation chromatography using polystyrene.

Comparative example

As the comparative example, ethyl cellulose resins STD-4 (The Dow Chemical Company) (R-1) and STD-100 (The Dow Chemical Company) (R-2) which are generally used as a resin binder were used.

Test Example 1

By using 2,2,4-trimethyl-1 from the (meth)acrylic resin of Examples 1 to 9 and ethylcellulose resin (STD-4 or STD-100 from The Dow Chemical Company), The 3-pentanediol monoisobutyrate solution was mixed to prepare a solution of the immediately thermally decomposable resin to provide a weight ratio of the solid ratio of the (meth)acrylic resin to the ethylcellulose resin of 20:80. This immediately thermally decomposable resin solution was coated on a glass plate with a 4 mil applicator, followed by drying to obtain a dried film of the immediately thermally decomposable resin. The results of observing the appearance of the dried film are shown in Table 1.

Based on the test results of Table 1, it can be concluded that the range of R ² in the (meth)acrylic resin of the formula (1) compatible with ethyl cellulose is a C _1-12 linear hydrocarbon group, a branch. a hydrocarbon group or a hydrocarbon group having a hydroxyl group, or a polyalkylene oxide-containing group.

Test Example 2

The dried film produced in Test Example 1 was subjected to thermal decomposition test using a TG/DTA apparatus (DTG-60A (from Shimadzu Corporation)) at a heating rate of 10 ° C/min under a nitrogen atmosphere using an aluminum bath, and the weight was measured. The temperature at which the reduction is at least 95% is regarded as the decomposition temperature. The residual carbon residue after the measurement was also evaluated. The results of the test are shown in Table 2.

The test results in Table 2 show that the immediate thermally decomposable resin according to the present invention has better thermal decomposition properties than the ethyl cellulose resin and is more advantageous for fire-bake applications.

Test Example 3

By using ethyl cellulose resin (STD-4 or STD-100 from The Dow Chemical Company) 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solution with and from implementation The methacrylic resins of Examples 10 to 14 were mixed to prepare a solution of the immediately thermally decomposable resin to provide a solid ratio of (meth)acrylic resin to ethylcellulose resin of 20:80. This immediately thermally decomposable resin solution was coated on a glass plate with a 4 mil applicator, followed by drying to obtain a dried film of the immediately thermally decomposable resin. The results of observing the appearance of the dried film are shown in Table 3.

Based on the test results of Table 3, it is understood that the (meth)acrylic resin capable of forming the immediate thermally decomposable resin according to the present invention preferably has a weight average molecular weight of not more than 200,000, depending on the appearance of the dried film.

Test Example 4

The dried film produced in Test Example 3 was subjected to thermal decomposition test using a TG/DTA instrument (DTG-60A from Shimadzu Corporation) at a temperature rising rate of 10 ° C/min under a nitrogen atmosphere, and the weight was lowered. The temperature at least 95% is regarded as the decomposition temperature. The residual carbon residue after the measurement was also evaluated. The results of the test are shown in Table 4.

Table 4 Thermal Decomposition of Dry Film from Immediate Thermally Decomposable Resin: Molecular Weight Test

The test results in Table 4 show that the immediate thermally decomposable resin prepared by Test Example 3 has better thermal decomposition properties than the ethyl cellulose resin, and is more advantageous for fire-bake applications.

Test Example 5

By using ethyl cellulose resin (STD-4 or STD-100 from The Dow Chemical Company) 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solution with and from implementation The methacrylic resin of Example 3 was mixed to prepare a solution of the immediately thermally decomposable resin to provide a solid ratio of (meth)acrylic resin to ethylcellulose resin of 5:95, 20:80, and 50: 50 weight ratio. This immediately thermally decomposable resin solution was coated on a glass plate with a 4 mil applicator, followed by drying to obtain a dried film of the immediately decomposable resin. The results of observing the appearance of the dried film are shown in Table 5.

Table 5 Appearance of dry film from immediate thermal decomposable resin: blending ratio test

Based on the test results of Table 5, it can be understood that a suitable mixing ratio of the (meth)acrylic resin and the ethylcellulose resin used for the instant thermally decomposable resin according to the present invention is a ratio of 5:95 to 50:50 (weight ratio) ).

Test Example 6

The dried film produced in Test Example 5 was subjected to thermal decomposition test using a TG/DTA apparatus (DTG-60A from Shimadzu Corporation) at a temperature rising rate of 10 ° C/min under a nitrogen atmosphere, and the weight was lowered. The temperature at least 95% is regarded as the decomposition temperature. The residual carbon residue after the measurement was also evaluated. The results of the test are shown in Table 6.

The test results in Table 6 show that the immediate thermally decomposable resin prepared by Test Example 5 has better thermal decomposition properties than the ethyl cellulose resin, and is more advantageous for applications requiring a fire baking step.

Test Example 7

Mixed silver fine powder (particle size = 3 μm), glass fine powder (particle diameter = 2 μm), solution of immediate thermal decomposable resin prepared as in Test Example 1 or Test Example 2, solvent (from KH Neochem Co., KYOWANOL M) of Ltd., and a dispersion (HIPLAAD ED 119 from Kusumoto Chemicals, Ltd.), and a high concentration silver particle dispersion having a composition as shown in Table 7 was obtained by dispersion using a roll mill.

Table 7 Composition of high concentration silver fine powder dispersion

The viscosity of the high concentration silver fine powder dispersion was measured at 25 ° C using an E-type viscometer and a 3° x R9.7 mm cone rotor. The TI (shake index) value represents the ratio of the viscosity at a shear rate of 0.4 [1/sec] to the viscosity at a shear rate of 4 [1/sec] at 25 ° C, that is, at the shear The viscosity at a cutting rate of 0.4 [1/sec] / the viscosity at a shear rate of 4 [1/sec]. The viscosity and T.I. values of the high concentration silver fine powder dispersion are shown in Table 8.

Using a stencil of #640 mesh having a line width of 50 μm, fine lines were printed on the ceramic substrate from the obtained high-concentration silver fine powder dispersion by screen printing, and by measuring the line width and line height of the printing and observing The state of printing is used to evaluate the characteristics of the high concentration silver fine powder dispersion. The results of the evaluation are shown in Table 8.

From the test results of Table 8, it is apparent that the high-concentration silver fine powder dispersion using the immediately thermally decomposable resin binder of the present invention has It has a viscosity-adjusting effect that is more suitable for screen printing than ethyl cellulose resin as a binder, and provides an excellent printing state.

[Industrial Application]

When the high concentration inorganic particle dispersion of the present invention is used in the production of electronic components such as circuits, electrodes, photovoltaic panels, microstrip antennas, capacitors, inductors, layered ceramic capacitors, plasma display panels, and the like, Printed patterns, such as specified interconnects, electrodes, resistive elements, capacitors, coils, etc., will improve the fire behavior and printing characteristics. Therefore, it is predicted that the present invention contributes to enhancing the characteristics of electronic components, and more particularly to mass production of electronic components, and saving energy in the process.

Claims (6)

An instant thermally decomposable organic resin binder comprising a (meth)acrylic resin and an ethylcellulose resin, the weight ratio between the (meth)acrylic resin and the ethylcellulose resin being 5:95 to Less than 50:50, wherein the (meth)acrylic resin is a (meth)acrylic polymer having a weight average molecular weight of 1,000 to 250,000 and consisting of monomer units represented by the following general formula (1) [In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents hydrogen or a C _1-12 linear hydrocarbon group, a branched hydrocarbon group, or a hydrocarbon group having a hydroxyl group, or a polyalkylene oxide group. -containing group)]. An immediate thermal decomposable organic resin binder according to claim 1, wherein R ¹ in the formula (1) is hydrogen or methyl, and R ² is C _1-4 alkyl, 2-ethylhexyl, lauryl, Hydroxyethyl, or methoxypolyethylene glycol. An immediate thermal decomposable organic resin binder according to claim 1, wherein the (meth)acrylic resin has a weight average molecular weight of 2,000 to 200,000. A high-concentration inorganic fine particle dispersion comprising inorganic fine particles and an immediate thermal decomposable organic resin binder as claimed in claim 1 as an essential component, and optionally comprising an organic solvent or an additive. a high concentration inorganic particle dispersion of claim 4, wherein the inorganic micro Granular silver particles. A functional paste composition comprising an immediate thermally decomposable organic resin binder as claimed in claim 1 and having excellent screen printing characteristics in a pattern forming process.